DFT and experimental studies on Rh(III)-catalyzed dual directing-groups-assisted [3+2] annulation and ring-opening of N‑aryloxyacetamides with 1-(phenylethynyl)cycloalkanol. (13th April 2021)

• Record Type: Journal Article
• Authors: Zhou, Jia; Li, Zi-Hao; Pan, Jin-Long; Chen, Chao; Ma, Xue-Feng; He, Yuhan; Ding, Tong-Mei; Zhang, Shu-Yu
• Is Part Of: Tetrahedron letters. Volume 69(2021)
• Publication Date: 2021-04-13
• Subjects: C-H activation and functionalization -- Rhodium catalysis -- Dual directing-groups -- Density functional theory calculation; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2021.152979
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Two different pathways have been ascertained to different products with DFT. The ring-opening or not in different cycloalkanols depended on their ring members. 4-membered ring was the critical structure for high ring strain and steric hindrance. Abstract: A density functional theory (DFT) has been conducted to elucidate the mechanism of N-aryloxyacetamides reacting with 1-(phenylethynyl)cyclobutanol and 1-(phenylethynyl)cyclopentanol under rhodium (III) catalysis. The impact of substrates with different ring numbers on the reaction mechanism has been discussed in detail. When the ring number exceeds 4, 1-(phenylethynyl)cycloalkanol simply conducts [3+2] annulation like the general reaction between N -aryloxyacetamides and alkyne. When the ring number is equal to 4, 1-(phenylethynyl)cyclobutanol undergoes cascade [3+2] annulation and ring-opening reaction via rhodium (III) catalysis. The results show that the ring-opening or not in 1-(phenylethynyl)cycloalkanol depends on ring members and the 4-membered ring is the critical structure for its high ring strain and steric hindrance.